CN114635116B - Corrosion-resistant antifriction anti-icing coating with multilevel structure and preparation method thereof - Google Patents

Corrosion-resistant antifriction anti-icing coating with multilevel structure and preparation method thereof Download PDF

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CN114635116B
CN114635116B CN202210299064.0A CN202210299064A CN114635116B CN 114635116 B CN114635116 B CN 114635116B CN 202210299064 A CN202210299064 A CN 202210299064A CN 114635116 B CN114635116 B CN 114635116B
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corrosion
substrate
sputtering
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icing
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CN114635116A (en
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崔洪芝
练晓娟
王全志
魏娜
宋晓杰
张春芝
张丽军
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Shandong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process

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Abstract

The invention discloses a corrosion-resistant antifriction anti-icing coating with a multilevel structure and a preparation method thereof, wherein the corrosion-resistant antifriction anti-icing coating is a surface of a substrate, a femtosecond laser processing technology is adopted to prepare a micron-sized rough texture with a bionic structure, then a magnetron co-sputtering TiAlCrNbZr alloy target and a simple substance target Cu or/and Ag are carried out to form a TiAlCrNbZrCu or/and Ag corrosion-resistant film with a nano-sized micro-convex structure, so that a film with a bionic multilevel structure of micron-sized and nano-sized is formed. The bionic multi-stage composite structure has good hydrophobicity, so that liquid drops roll off on a hydrophobic surface before icing, icing is prevented, dirt adhesion is prevented, and antifouling and anti-icing are realized; meanwhile, cu and Ag elements distributed on the nanometer microprotrusions play a role in sterilizing by reducing the adhesion of microorganisms and by virtue of the nanometer microprotrusions, so that the Cu or Ag element and bionic multi-stage composite structure can synergistically improve the hydrophobic, antifouling and anti-icing effects of the film.

Description

Corrosion-resistant antifriction anti-icing coating with multilevel structure and preparation method thereof
Technical Field
The invention relates to the field of material surface treatment, in particular to a film with a bionic multi-stage composite structure of micron-level rough textures and nanometer-level micro-protrusions, which is formed on the surfaces of stainless steel, titanium alloy, aluminum alloy, copper alloy and magnesium alloy, so that the binding force is improved, the corrosion resistance, antifriction, hydrophobicity, antifouling and anti-icing performances are improved, and the film is suitable for surface protection of key parts in the fields of maritime work, nuclear power, electric power, high-speed rail, aviation and the like.
Background
In the fields of maritime work, nuclear power, electric power, high-speed rail, aviation and the like, a large number of equipment key parts are corroded and worn, the surfaces are stained, frozen and the like, so that the service life is greatly shortened, and potential safety hazards are brought to running and running. The method for forming the wear resistance and corrosion resistance on the surface is commonly used at present: laser cladding, thermal spraying, vapor deposition, ion implantation, etc., can be used to prepare coatings of different properties on different metallic material substrates.
Chinese patent application No. 202110658706.7 provides a Cr 3 C 2 Preparation method of reinforced NiCrMoW antifriction wear-resistant corrosion-resistant coating, wherein the coating comprises 70-85% by mass of metal phase NiCrMoW and 15-30% by mass of ceramic reinforced phase Cr 3 C 2 The coating obtained by spraying the atmospheric plasma spraying technology on the substrate can store lubricating oil by controlling the preparation process parameters, 4-7% of pores are reserved in the coating, the friction coefficient can be greatly reduced, and the coating has high bonding strength while maintaining the excellent wear resistance and corrosion resistance.
Wear-resistant corrosion-resistant material
Chinese patent application No. 201610006219.1 discloses a cold spray self-lubricating abrasion-resistant aluminum-based coating composition and a preparation technique thereof, wherein the coating comprises Al and Al 2 O 3 And M is a combination of aluminum rare earth alloy and/or aluminum magnesium alloy and molybdenum disulfide and/or tungsten disulfide. The prepared aluminum-based self-lubricating abrasion-resistant coating has better abrasion resistance and local corrosion resistance, can fully protect a marine steel structure and prolongs the service life of the marine steel structure.
Chinese patent application number 202110857126.0 discloses a bio-friendly corrosion-resistant wear-resistant titanium-based coating, a preparation method and application thereof, wherein the composition of the corrosion-resistant wear-resistant titanium-based coating is TiZrNb, the content of Ti element in the TiZrNb coating is 70-80%, the sum of the content of Zr element and Nb element is 20-30%, and the content of Zr element and Nb element is equal. By adding Zr and Nb elements into the Ti-based alloy, the corrosion resistance and the wear resistance of the coating are improved, and simultaneously, three elements of Ti, zr and Nb are biologically friendly and nontoxic. Therefore, the Ti-based alloy containing Zr and Nb elements is prepared into a coating material, and can provide a new choice for the field of surface modification of medical implant materials.
The Chinese patent application number 202111006130.2 provides a femtosecond laser processing method of an optical fiber surface cladding micro-nano structure, and the femtosecond laser has obvious advantages for processing the surface micro-structure of the hard and brittle material and the curved surface part of the single crystal optical fiber due to the ultra-strong and ultra-fast characteristic, and the method greatly improves the positive correlation between the laser focal spot and the focal depth and the nonlinear effect caused by the energy distribution along the optical axis, thereby being beneficial to generating the micro-structure with large depth-to-diameter ratio on the surface of the optical fiber.
Chinese patent application No. 202111127188.2 discloses a magnetron sputtering biomedical multi-stage structural film, wherein the transition layer is a Ti, zr, ta layer, and the service layer (exposed layer/outermost layer) is a tantalum coating. And respectively installing a plurality of targets on different targets in a magnetron sputtering instrument, and controlling the sputtering sequence of the different targets according to the specific structural layers of the multi-stage structural film so as to control the deposition thickness of each film layer in a single modulation period, thereby finally obtaining the required multi-stage structural film. The advantages are that: the coating is nontoxic, nonmagnetic, strong in corrosion resistance, favorable for being used as a biomedical film layer and belongs to a biological functional film.
The patent improves the wear resistance and corrosion resistance of the surface of the key part material to a certain extent, but aiming at the comprehensive performance requirements of corrosion resistance, antifriction, hydrophobicity, antifouling property, icing resistance and the like, a film layer with strong binding force and low stress is prepared, and the report of the related technical invention is not seen.
Disclosure of Invention
In order to improve the service life of some equipment key parts in the fields of maritime work, nuclear power, electric power, high-speed rail, aviation and the like, the invention provides the corrosion-resistant antifriction anti-icing coating with a multilevel structure, which is firmly combined and has comprehensive performances of corrosion resistance, antifriction, hydrophobicity, pollution resistance, anti-icing and the like.
The invention also provides a preparation method of the corrosion-resistant antifriction anti-icing coating with the multilevel structure
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a corrosion-resistant antifriction anti-icing coating with a multilevel structure is characterized in that the corrosion-resistant antifriction anti-icing coating is a surface of a substrate, a femtosecond laser processing technology is adopted to prepare a micron-sized rough texture with a bionic structure, then a magnetron co-sputtering TiAlCrNbZr alloy target and an elemental target Cu or/and Ag are carried out to form a TiAlCrNbZrCu or/and Ag corrosion-resistant film with a nanometer-sized micro-convex structure, so that a film with a bionic multilevel structure of micron-sized and nanometer-sized is formed.
Further, the biomimetic structure includes wavy, vermiform, braided, leopard-like, fish scale-like and tortoise-like.
Further: the TiAlCrNbZr alloy target is prepared according to the mol ratio of 1:1:1:1: the ratio of (0-1) is obtained by vacuum melting.
The invention provides a method for preparing the corrosion-resistant antifriction anti-freezing coating with the multilevel structure, which specifically comprises the following steps:
step 1: substrate pretreatment
Polishing and cleaning the substrate to remove surface organic matters and impurities
Step 2: machining micro-scale rough textures on a substrate using femtosecond laser
Setting a laser scanning track according to the performance requirement of a substrate, scanning the surface of the substrate by using a 3W femtosecond laser to prepare a sample with a micron-sized characteristic texture structure, wherein the spot diameter of the laser is 3mm, the pulse width is less than 270fs, the femtosecond laser processing parameters are adjusted, the laser power is 45mW-1.3W, and the scanning interval is 10um-30um;
step 3: preparation of TiAlCrNbZrCuAg nano-scale micro-convex structure film by magnetron sputtering
Firstly, clamping a substrate subjected to femtosecond laser processing on an objective table in an unbalanced magnetron sputtering cavity, and introducing high-purity Ar gas for pre-sputtering after the cavity reaches vacuum degree to remove impurities and residues on the surface of the substrate; further: when the vacuum is pumped, firstly, mechanically pumping the rough vacuum to 10Pa, then, utilizing the molecular pump to high the vacuum to 3.5X10-3 Pa, and after the high vacuum degree is reached in the cavity, introducing 30sccm high-purity Ar gas to perform pre-sputtering for five minutes;
then sputtering TiAlCrNbZr alloy target and Cu or/and Ag simple substance metal target by direct current, wherein the TiAlCrNbZr alloy target is prepared according to the mol ratio of 1:1:1:1: the ratio of (0-1) is obtained by vacuum melting; the magnetron sputtering parameters are as follows: the heating temperature of the substrate is 100-300 ℃, the rotating speed of the circular object stage is 5-60rpm, the power of the TiAlCrNbZr alloy target is 100-200W, the power of the Cu and Ag elemental metal target is 50-200W, the sputtering time is 30-180min, and the sputtering pressure is 0.9-1.2Pa; by controlling the different sputtering powers and sputtering times, a coating of the desired deposition thickness is obtained.
It should be noted that: the Cu and Ag simple substance targets can be two single targets, or Cu and Ag can be mixed into a composite target in advance according to the proportion, the composite proportion is selected according to the material performance, but the target power is 50W-200W no matter whether the targets are two single targets or one single target.
(1) The invention regulates and controls the micro bionic rough texture structure of the base material by femtosecond laser processing, is quick and simple, can form different texture structures on the surfaces of different metals such as stainless steel, titanium alloy, aluminum alloy, copper alloy, magnesium alloy and the like, obviously enhances the interface combination between a substrate and a coating, and is beneficial to the falling off of dirt and ice coating.
(2) The invention can obtain different wear resistance, corrosion resistance, antifriction performance coordination and thickness by adjusting the components and the power of the TiAlCrNbZr alloy target and the Cu and Ag single metal targets, thereby meeting the different application scenes of maritime work, nuclear power, electric power, high-speed rail, aviation and the like.
(3) The micron-sized rough texture with the bionic structures such as wavy, worm-shaped and woven structures and the multi-stage composite structure film with the nano-sized micro-convex structures can achieve the effects of hydrophobicity, antifouling and anti-icing, reduce the tensile stress formed in the film preparation process and avoid the cracking of the film.
(4) The invention prepares the nano-scale micro-convex structure film by utilizing alloy powder and single powder formed by dulling elements such as TiAlCrNbZr and the like through magnetron co-sputtering, and the amorphous nano-crystal micro-convex structure formed by the dulling elements such as TiAlCrNbZr and the like in the process improves the corrosion resistance and the wear resistance of the film layer; the Cu and Ag soft metals are distributed in the hard metal film layers such as TiAlCrNbZr, and when in friction and wear, the friction and wear can be relieved by changing the sliding friction deformation of the surface of the material through soft deformation and falling off, so that the friction deformation is prevented from being brought to a deeper depth and a larger range of the material, the surface of the material is severely worn, the friction and wear resistance effects are achieved, meanwhile, the friction and wear resistance effects are cooperated with a bionic multi-stage composite structure, the hydrophobic, antifouling and anti-icing effects of the film layer are improved, and the cooperated and cooperated mechanism is as follows: the bionic multi-stage composite structure has good hydrophobicity, so that liquid drops roll off on a hydrophobic surface before icing, icing is prevented, dirt adhesion is prevented, and antifouling and anti-icing are realized; meanwhile, cu and Ag elements distributed on the nanometer microprotrusions are used for reducing the adhesion of microorganisms and playing a role in sterilization by virtue of the nanometer Cu and Ag elements. Therefore, the Cu or Ag element and the bionic multi-level composite structure can synergistically improve the hydrophobic, antifouling and anti-icing effects of the film.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed for the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram of a micro-topography of a woven texture produced by a femtosecond laser on a stainless steel substrate surface;
FIG. 2 shows a microscopic morphology diagram of a magnetron sputtering TiAlCrNbZrCu nano micro-protruding film after a stainless steel substrate is processed with micro-textures;
FIG. 3 is a diagram of an amorphous-nanocrystalline structure of the TiAlCrNbZrCu film of the invention using different power magnetron sputtering;
FIG. 4 is an electrochemical polarization curve of the stainless steel substrate TiAlCrNbZrCu film obtained in FIG. 3 according to the present invention;
FIGS. 5a-5d are the hydrophobicity of a stainless steel substrate TiAlCrNbZrCu film obtained when the molar ratio of Zr in the alloy target of the present invention is 0,0.3,0.6,1.0, respectively;
FIG. 6 is a diagram of a worm-like texture micro-topography prepared by femtosecond laser on a titanium alloy substrate surface according to the present invention.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the accompanying drawings and examples so that advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present invention.
Embodiment one: preparation of TiAlCrNbZrCu nano-scale micro-convex structure film on 304 stainless steel
Step 1: substrate pretreatment
The base material is made of 304 stainless steel, and is sequentially ground and polished by 200# sand paper, 400# sand paper, 800# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper; sequentially carrying out ultrasonic cleaning for 15 minutes by using acetone, ethanol and deionized water to remove organic matters and impurities on the surface.
Step 2: processing braided micron-sized rough texture on surface of base material by femtosecond laser
The pretreated 304 stainless steel substrate is placed on a sample object stage, and a 3W femtosecond laser is used for scanning and processing a woven texture on the surface of the 304 stainless steel (see figure 1), the diameter of a light spot is 3mm, the laser power is 47mW, and the scanning interval is 10um.
Step 3: preparation of TiAlCrNbZrCu nano-scale micro-convex structure film by magnetron co-sputtering
The 304 stainless steel base material processed by femtosecond laser is clamped on a circular objective table in an unbalanced magnetron sputtering cavity, coarse vacuum is pumped to 10Pa by a mechanical pump, and high vacuum is pumped to 3.5 multiplied by 10- 3 Pa, introducing 30sccm high-purity Ar gas after the high vacuum degree is reached in the cavity, pre-sputtering for five minutes, and removing impurities and residues on the surface of the substrate;
then, utilizing the surface of a double-target direct current magnetron sputtering substrate, wherein targets are respectively a TiAlCrNbZr alloy target and a Cu simple substance metal target, and the purities of the targets are 99.99%, wherein the TiAlCrNbZr alloy target is prepared according to a molar ratio of 1:1:1:1: the 0-1 proportion is obtained by vacuum smelting, and the technological parameters are as follows: the alloy target power is 120W, the single metal target power is 80W, the substrate heating temperature is 100 ℃, the rotating speed of the circular object stage is 20rpm, the sputtering pressure is 1.1Pa, the sputtering time is 40min, and finally the TiAlCrNbZrCu nano-scale micro-convex structure film is obtained.
In order to verify the influence of Zr content in the alloy target on film performance, in the first embodiment, the Zr molar ratio doping amounts are respectively taken according to 0,0.3,0.6,1.0, and the test results obtained by the four doping amounts are respectively shown in fig. 3-5.
Testing the TiAlCrNbZrCu film layer prepared in the first embodiment:
(1) The surface morphology of the femtosecond laser processed 304 stainless steel substrate was observed by a scanning electron microscope, and as shown in fig. 1, the 304 stainless steel surface exhibited a woven micron-sized rough texture.
(2) The surface of the 304 stainless steel band with the knitting micron-sized rough texture is subjected to magnetron sputtering plating of TiAlCrNbZrCu film, as shown in figure 2, the surface is uniform and compact, and the nanometer-sized micro-convex structure is clearly visible (see the insert diagram at the upper right corner of figure 2)
(3) The magnetron sputtering TiAlCrNbZrCu film on the surface of 304 stainless steel is subjected to phase analysis, the analysis result is shown in figure 3, the raised steamed bread peak can be seen on the XRD map of figure 3, the amorphous structure is represented, the diffraction peak with wide half peak width and low diffraction intensity appears along with the addition of Zr and the increase of Zr content, the nanocrystalline is represented, the amorphous and nanocrystalline coexist in the prepared TiAlCrNbZrCu film layer, the hardness and the wear resistance of the grinding layer are improved, the stress of the grinding layer is reduced, the nano micro-convexity is formed, and the functions of hydrophobicity, antifouling property, anti-icing and the like are realized.
(4) The electrochemical test was performed on the magnetron sputtered TiAlCrNbZrCu film on the 304 stainless steel surface, and as shown in fig. 4, the passivation region was widened, the vickers current was reduced, and it can be seen that the corrosion resistance of the TiAlCrNbZrCu film was improved, and the corrosion resistance was better with the improvement of the Zr element ratio.
(5) From fig. 5a, 5b, 5c and 5d, it is seen that the stainless steel surface obtained when the Zr molar ratio is 0,0.3,0.6,1.0 has a woven micron-sized rough texture, and the nano-sized magnetron sputtering TiAlCrNbZr film shows hydrophobicity and good anti-fouling and anti-freezing effects.
Embodiment two: preparation of TiAlCrNbZrAg nano-scale micro-convex structure film on TC4 titanium alloy substrate
Step 1: substrate pretreatment
Selecting TC4 titanium alloy as a base material, and sequentially polishing with 200# sand paper, 400# sand paper, 800# sand paper, 1500# sand paper, 2000# sand paper and 2500# sand paper; sequentially carrying out ultrasonic cleaning for 15 minutes by using acetone, ethanol and deionized water to remove organic matters and impurities on the surface.
Step 2: processing worm-like texture on substrate surface using femtosecond laser (see FIG. 6)
Placing the pretreated TC4 titanium alloy substrate on a sample object stage, and scanning and processing a braided texture on the surface of the TC4 titanium alloy substrate by using a 3W femtosecond laser (see figure 6), wherein the diameter of a light spot is 3mm, the laser power is 1.3W, and the scanning interval is 10um;
step 3: preparation of TiAlCrNbZrAg nano-scale micro-convex structure film by magnetron co-sputtering
Clamping the TC4 titanium alloy substrate processed by femtosecond laser on a circular objective table in an unbalanced magnetron sputtering cavity, mechanically pumping coarse vacuum to 10Pa, and then utilizing a molecular pump to high vacuum to 3.5 multiplied by 10- 3 Pa, introducing 30sccm high-purity Ar gas after the high vacuum degree is reached in the cavity, pre-sputtering for five minutes, and removing impurities and residues on the surface of the substrate;
then, the surface of a double-target direct current magnetron sputtering substrate is utilized, the targets are respectively a TiAlCrNbZr alloy target and an Ag single metal target, the purities of the targets are 99.99%, and the TiAlCrNbZr alloy target is prepared according to the molar ratio of 1:1:1:1: the proportion 1 is obtained by vacuum smelting, and the technological parameters are as follows: the TiAlCrNbZr alloy target power is 150W, the Ag target power is 100W, the substrate heating temperature is 200 ℃, the rotating speed of the circular object stage is 30rpm, the sputtering pressure is 0.9Pa, the sputtering time is 60min, and finally the TiAlCrNbZrAg nano-scale micro-convex structure film is obtained.
The tialcrnbzragg film prepared in example two was tested:
(1) the surface morphology of the femtosecond laser processed TC4 titanium alloy substrate was observed by a scanning electron microscope, and as shown in FIG. 6, the TC4 titanium alloy surface exhibited worm-like micron-sized rough textures.
(2) The other components are amorphous and nanocrystalline structures, good corrosion resistance, hydrophobicity, pollution resistance and ice resistance, and the friction coefficient is reduced from 0.35 to 0.20, so that the micro-nano morphology of the femtosecond laser processing substrate has an influence on the antifriction effect, the micro-nano morphology of the substrate is different, the matching of the film and the substrate is different, and the antifriction effect is different.

Claims (5)

1. A corrosion-resistant antifriction anti-icing coating with a multilevel structure is characterized in that the corrosion-resistant antifriction anti-icing coating is a surface of a substrate, a femtosecond laser processing technology is adopted to prepare a micron-sized rough texture with a bionic structure, then a magnetron co-sputtering TiAlCrNbZr alloy target and an elemental target Cu or/and Ag are carried out to form a TiAlCrNbZrCu or/and Ag corrosion-resistant film with a nanometer-sized micro-convex structure, so that a film with a bionic multilevel structure of micron-sized and nanometer-sized is formed.
2. The corrosion-resistant friction-reducing anti-icing coating of a multi-stage structure according to claim 1, wherein said biomimetic structure comprises waves, worms, braids, leopards, fish scales and tortoises.
3. The multi-level structured corrosion-resistant antifriction anti-icing coating of claim 1 wherein said TiAlCrNbZr alloy target is in a molar ratio of 1:1:1:1: the ratio of (0-1) is obtained by vacuum melting.
4. A method for preparing a corrosion-resistant antifriction anti-freeze coating of a multi-stage structure according to any one of claims 1 to 3, characterized in that it comprises in particular the following steps:
step 1: substrate pretreatment
Polishing and cleaning the substrate to remove surface organic matters and impurities;
step 2: machining micro-scale rough textures on a substrate using femtosecond laser
Setting a laser scanning track according to the performance requirement of a substrate, scanning the surface of the substrate by using a 3W femtosecond laser to prepare a sample with a micron-sized characteristic texture structure, wherein the spot diameter of the laser is 3mm, the pulse width is less than 270fs, the femtosecond laser processing parameters are adjusted, the laser power is 45mW-1.3W, and the scanning interval is 10um-30um;
step 3: preparation of TiAlCrNbZrCu or/and Ag nano-scale micro-convex structure film by magnetron sputtering
Firstly, clamping a substrate subjected to femtosecond laser processing on an objective table in an unbalanced magnetron sputtering cavity, and introducing high-purity Ar gas for pre-sputtering after the cavity reaches vacuum degree to remove impurities and residues on the surface of the substrate; then sputtering TiAlCrNbZr alloy target and Cu or/and Ag simple substance metal target by direct current, wherein the TiAlCrNbZr alloy target is prepared according to the mol ratio of 1:1:1:1: the ratio of (0-1) is obtained by vacuum melting; the magnetron sputtering parameters are as follows: the heating temperature of the substrate is 100-300 ℃, the rotating speed of the circular object stage is 5-60rpm, the power of the TiAlCrNbZr alloy target is 100-200W, the power of the Cu and Ag elemental metal target is 50-200W, the sputtering time is 30-180min, and the sputtering pressure is 0.9-1.2Pa; by controlling the different sputtering powers and sputtering times, a coating of the desired deposition thickness is obtained.
5. The method for producing a multi-stage corrosion-resistant antifriction anti-freezing coating according to claim 4 wherein step 2 is performed by pumping rough vacuum to 10Pa and then pumping high vacuum to 3.5X10 s by molecular pump -3 Pa, after the high vacuum degree is reached in the cavity, introducing 30sccm high-purity Ar gas for pre-sputtering for five minutes.
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